There are a number of applications where it is necessary to bond materials together using adhesives and it is undesirable for the adhesive to give off any volatile organic materials after cure. The process of evolving volatile organic materials after cure is often called outgassing or offgassing. Examples of such applications are in the area of food packaging where the outgassed compounds can impart an off-taste to the packaged food material. In the area of optics and photonics, outgassed compounds can condense on optical surfaces and negatively affect the transmission of light.
For many adhesive or lens potting applications, it is necessary to bond together materials (substrates) of different coefficients of thermal expansion. In these applications, the adhesive or potting material must allow for the expansion and contraction of the two different substrates as the temperature changes yet still maintain the adhesion of the two substrates together. This requires the use of a soft, low modulus, low Tg rubbery type material. The ability to formulate materials that cure to soft, compliant, rubber-like solids and yet still have low outgassing after cure is very difficult. This is especially true if the cured material also has to have excellent thermal, oxidative and hydrolytic stability.
Many room temperature vulcanized (RTV) silicone materials cure to soft, compliant rubber-like solids that have good thermal, oxidative and hydrolytic stability but they still evolve an unacceptable amount of volatiles after cure. The outgassed products of the RTV silicones are usually low molecular weight, sometimes cyclic, siloxanes. These materials are particularly problematic because if they condense on surfaces, they are difficult to remove due to their very low surface tension. Contamination of optical surfaces by those products is especially a concern when RTV silicones are used as adhesive or lens-potting material in optical devices where high irradiation fluence and/or short wavelength irradiation is used. Such surface contamination is highly undesirable and should be avoided in precision optical systems, such as inspection systems used in the semiconductor industry, for example, a lithographic inspection system.
Other materials often considered are polysulfides, polyurethanes, and hydrocarbon rubbers like polybutadiene, polyisoprene, etc. These products do not possess sufficient thermal, oxidative and hydrolytic stability for applications where the rubbery material must remain rubbery throughout its entire lifetime which may be as long as 30 years. Such applications are in the optics and photonics area where in order to simulate 30 year lifetime, materials are subjected to various accelerated aging tests like exposure to conditions of 85° C. and 85% RH for a minimum of 500 hours and up to as long as 2000 hours.
It is also advantageous for the material to be curable with actinic radiation such as UV or visible light or an electron beam. This enables the material to be applied as a liquid, then optical alignments, or other positional adjustments can be made. When the adherends are in their optimized position, the actinic radiation can be turned on which cures the materials quickly (within seconds or minutes) and with minimal amount of heat. This process retains the delicate alignment of the adherends.
Engineering solutions have been proposed to eliminate or mitigate the outgassed products from adhesives. These involve novel joint designs that allow for elimination of the outgassed materials from the adhesive into non-sensitive areas (JP 2001155855 and JP 2002106719). In another case, the surface of the adhesive material is coated with an impervious inorganic layer that seals in possible outgassed products (US2001028062). Other methods involve heat and/or vacuum treatments of the cured adhesive to remove possible outgassed products prior to final assembly of the device. All of these methods require extra steps that are unnecessary if a true low outgassing adhesive, sealant, or potting compound were available.
JP 2002146230 by H. Kawakami et al. describes an adhesive composition that is for semiconductor-mounted circuit boards and devices therewith. This composition gives a B-stage adhesive film containing less volatile components. However, the composition is not UV curable, contains MEK solvent, and is based on bisphenol A epoxy and phenolic resins which require heat to cure and cure to hard, non-flexible, thermoset polymers.
E. A. Boulter et al. claims zero volatile release from their high service temperature polyether amide thermoset resins. These materials are not UV curable and require a cure schedule of 1 hour at 177° C. followed by a postcure at 225° C. The final cured properties resemble that of cured bisphenol A type epoxies. See E. A. Boulter, M. Cohen, M. L. Deviney, Proceedings of the Electrical/Electronics Insulation Conference (1997), 23rd, 249-53.
JP 2001164737 by I. Tanaka et al. describes using low out-gas adhesives to make floor sheets useful for clean rooms. The adhesives are of the two component epoxy resin-polyamideamine class. Such materials require the mixing of the two parts (an extra manufacturing step), are not photocurable, and cure to form polymers that are not low Tg rubbers.
JP 2001057065 by K. Fukuda et al. describes sealant compositions for computer hard disc drives that claim no gas volatilization, good sealability and adhesive strength. EP302620 by G. M. Vanhaeren describes a crosslinkable hot-melt adhesive containing a polyol and a blocked isocyanate that provides a flexible heat-resistant bond without forming volatiles. However, both of the above materials must be applied as hot melts and the high temperatures involved would negatively affect the delicate alignment required for many optical devices.
R. C. Benson et al. and C. T. Mooney et al. investigated the measurement of volatile organic species that evolve during cure and after post-cure processing of epoxy or polyimide based die attach adhesives. Similar studies were performed by R. C. Benson et al. on adhesives for microelectronics. These formulations are not photocurable and also do not cure to the soft rubbery type polymers required for the application. See R. C. Benson, T. E. Phillips, N. DeHaas, Proc.-Electron. Compon, Conf. (1989), 39th, 301-08. See also R. C. Benson, T. E. Phillips, N. DeHaas, M. Bonneau, Int. SAMPE Electron, Conf. (1990), 4 (Electorn). Mater.-Our Future), 267-81. See also C. T. Mooney, J. C. Bolger, Natl. SAMPE Symp. Exhib., [Proc.], (1984), 29th (Technol. Vectors), 639-50.
R. Leoni describes adhesives that have very low emissions of volatile organic compounds. Such adhesives are high tack, contact adhesives intended for floor coverings, tiles, carpets, vinyl sheeting, etc. These materials are not photocurable and are not suitable for this application due to their permanent tackiness. See R. Leoni; FATlPEC Congress (2000), 25th (Vol. 1), 253-265.
J. Kuczynski studied the possibility of eliminating the outgassing from UV curable adhesives. Such outgassed products were shown to corrode thin film magnetic discs. The volatility of the corrosive species was dependent on the adhesive's glass transition temperature which varied linearly with flexibilizer concentration. Thermogravimetric analysis revealed that outgassing was reduced an order of magnitude in adhesives containing reduced concentrations of polycaprolactone based flexibilizer. See J. Kuczynski, J. of Adhesion (1996), 56 (1-4), 107-119. For the current application, it is desirable to simultaneously have a low Tg and low outgassing. Also, polycaprolactone type materials are undesirable due to their inherent hydrolytic instability.
Finally, JP 2001163931 by Y. Arai and T. Nemoto describes photocurable sealing compositions generating a reduced amount of volatile gas for electronic devices. Such compositions are based on a high MW (˜50,000) urethane (meth)acrylate synthesized from a polypropylene glycol extended bisphenol A diol, tetrahydrofurfuryl acrylate, and phenoxy ethyl acrylate. Such compositions would not have the outstanding thermal and oxidative stability or the higher, inherent hydrophobicity of the present invention.
There remains a genuine need of an adhesive material that is photo or electron beam curable, and that upon being cured forms a material with low outgassing rate, low modulus and low Tg that is suitable for use in, inter alia, the optics area. There also remains a genuine need of devices, especially optical devices, comprising such cured adhesive material.